Journal of Materials Science and Engineering A 1 (2011) 857-864 Formerly part of Journal of Materials Science and Engineering, ISSN

1934-8959

DA VID

PUBLISHING

Nanogold Synthesis Using Matrix Mono Glyceryl Stearate as Antiaging Compounds in Modern Cosmetics
Titik Taufikurohmah1, I Gusti Made Sanjaya1 and Achmad Syahrani2
1. Chemistry Department, the State University of Surabaya, Surabaya 60231, East Java, Indonesia 2. Pharmacy Department, Airlangga University, Surabaya East Java, Indonesia Received: August 01, 2011 / Accepted: September 06, 2011 / Published: November 10, 2011. Abstract: Synthesis of nanomaterials through a bottom up process generally constrained on various factors such as temperature, stirring speed, concentration of reagents, concentration of reductors and thermodynamic conditions. To cope these obstacles, nanomaterials synthesis of gold (nanogold) was attempted using matrix as a barrier to the growth of gold clusters that tend to uncontrollably. The growth of gold clusters uncontrolled causes the nano size exceeded and further aggregation becomes uncontrollable. Such conditions are evident from the occurrence of large-sized sediment from the synthesis results which far exceeds the nano size. The synthesis uses raw materials HAuCl4 1 mM, the reducing agent Sodium Citrate 1% and matrix mono glyceryl stearate 0.2% which is one of the basic constituent in a cosmetic cream. Utilization of nanogold in cosmetics was preceded by preliminary research showing that the nanogold safe for cosmetic. The synthesis carried out at a temperature of 80 C with stirring 300 rpm for 20 min. The results of synthesis which was observed using instrument of SEM-EDX showed that the synthesis has a similar morphology to previous studies (standard). Thus, it was concluded that the synthesis of nanogold done with the conditions as described above is successful. Key words: Synthesis, nanogold, matrix, cluster, cosmetics.

1. Introduction
Nanomaterial synthesis is generally divided into two kinds of processes, namely the top down and the bottom up. Top down process is the process of making nanomaterials from big initial material into small-sized nanomaterials. While the bottom up process is the process of making nanomaterial from small initial material, i.e., ionic or atomic-sized materials into big size nanomaterials [1]. Nanomaterial synthesis in this research is to use the bottom up by changing the raw materials HAuCl4 into nanogold, which are bigger in size. Reducing reagent is sodium citrate with a concentration of 1% which is made by dissolving 1 g of sodium citrate in 100 mL of aquades. Gold solution (HAuCl4) with a concentration of 1 mM is made by dissolving 1 g of gold with 8 mL of

Corresponding author: Titik Taufikurohmah, research field: nano science. E-mail: titiksst@yahoo.co.id.

aquaregia, then diluted with aquades to 1,000 mL. The resulting gold solution of 5 mM and then diluted 5 times to get the concentration of 1 mM [1]. Basically, the solution of HAuCl4 produces chloroauric ion or AuCl4- in solution which reduces to Au in the synthesis with the presence of sodium citrate as a reducing agent. Gold atoms are joined to each other and grow uncontrollably, so when it has achieved a big cluster and then falls as precipitation. When this occurs, the size of the nanomaterial is exceeded and is not produced the desired nano-scale materials. To solve this problem, use a matrix that would block the uncontrolled growth of these clusters [1]. Matrix used in the research is glyceryl mono stearate, a compound of ester formed from glycerol and a stearic acid. This matrix will inhibit the formation of gold clusters that are naturally sustainable. This inhibition causes the absence of gold deposits produced in this synthesis. This is in accordance with the desired,

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Nanogold Synthesis Using Matrix Mono Glyceryl Stearate as Antiaging Compounds in Modern Cosmetics

i.e., the formation of material of nanogold. Stirring also helps the growth of gold clusters in which the agitation will increase the kinetic energy of particles in the system. Similarly, warming also increases the kinetic energy of particles thus allowing the occurrence of collisions between particles which is the beginning of chemical reaction [2]. Temperature and stirring speed affects the speed of reaction. Both are controlled in this research, the reaction temperature -80 C and stirring speed 300 rpm. The concentration of the matrix as a barrier to the growth of nanogold cluster is also controlled in a concentration of 0.2%. Matrix is added in the solution of gold before the reducing agent is inserted. This is done because of the reduction process takes place very rapidly. When both are added simultaneously or after reducing agents met with HAuCl4-, then the reduction process is difficult to control, and precipitate suddenly formed [3]. Glyceryl monostearate matrix that is used is one of the basic constituent materials in cosmetic cream. Nanogold bound in this material will be used in modern material of anti-aging cosmetic along with other cosmetic. Nanogold serves as a catalyst the formation of collagen, helping enzymes that already exist in the system, metabolism of collagen formation by skin cells. Mechanism of the formation of collagen synthesis is based on the ability of gold or nanogold in attractive electron-electron as the beginning of the chemical reaction. One species electron with another species in a system coupled to perform the reaction, henceforth when a bond has formed the gold or nanogold out of the reaction and will perform the same task for the next spec-spec. So forth so that all species in the reacting system becomes more complex material [2]. The use of gold in human life have began centuries ago that is as jewelry, gold coins, medals, monuments and plate coating of pure gold for the deposits of high economic value. The whole society has known gold in daily life in the form of jewelry. Other uses of gold as an essential material in cosmetics, is still less

popular [4]. Modern cosmetic uses of gold as an anti-aging material mainly because gold becomes a catalyst in the formation of collagen. Collagen is one of the major protein constituent of skin tissue. Regeneration of collagen regularly makes collagen tissue of the skin to become solid so that skin becomes firmer and look younger. Conversely, if growth is not balanced with the damage of collagen, the skin looks wrinkled and old impressed. The catalyst used in the formation of collagen in the previous cosmetic is vitamin C, which has a weakness stinging on the skin and the activity easily decreased. The gold materials can overcome these weaknesses. Recent developments of anti-aging cosmetic by using gold nanoparticles need to be further developed to obtain optimum catalytic effect [5]. In macro-micro size particles of gold atoms are numbered in the hundreds to thousands of stacked so that each atom cant perform its function with the maximum. To optimize the benefits of gold in the form of cosmetic innovation needs to be done is to create a cluster of gold through a synthesis with the basic material comes from the shape of metal cations to make nano-size gold or better known as gold nano-particles or nanogold. In the form of clusters or nanogold each gold atom with a certain amount to perform the function more optimally in a geometry where there is no buildup of atoms [6]. Basically, gold can be used as an anti-aging in cosmetics because gold is an effective catalyst for the formation of C-O C-H, C = O, C-C, and N-H bonds. It is the basis of the existing bond exception to the membrane protein collagen which is the main and largest constituent of skin layers. Thus whenever there is damage to skin cells a new skin will be immediately formed an younger, more elastic and white, because it has not formed pigmentation due to sunlight. The cell regeneration can take place faster than the skin will look younger and faster [7-9]. Innovation efforts are very important because the size of nanogold in the form of nano-gold is optimal

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catalytic ability, caused by increasing surface area in contact with the substrate. Optical properties of gold have also changed drastically which form nano provides a transparent color so that no more yellow as in the form of bulky. Synthesis of nanogold needs to be done with cosmetic material as the matrix. Gold ions with a certain concentration will be reduced to atomic form. These atoms will soon come together and form a precipitate if it is not immediately tied to a particular matrix. Matrix in question is glyceryl monostearate which is one of the basic constituent cream will bind 30-100 gold atoms for nano form can be generated. Synthesis performed in solution of hot gold cations in which there is a matrix which will solidify at room temperature. Sodium citrate solution is a reducing cation gold. Stirring, heating, pressure, concentration of gold ions, the concentration of the matrix and the number of kilns are the factors that affect the synthesis of this nanogold [2]. Nanogold catalyst having catalytic ability is much greater than the material in the form of solid gold. Thats why a synthetically nanogold effort is done to get the highest catalytic effect of its use in cosmetics. Utilization of metallic gold in cosmetics has been tested for safety by testing methods Protein Denaturation. This preliminary test also tested some heavy metals which are very unsafe for the skin such as Mercury, Lead and Cadmium. Metal safe for cosmetics is that a metal does not mendenaturasi protein [10]. In this test used protein albumin from egg white diluted with aquades. Nanogold and differen form of gold HAuCl4 do not show protein denaturation. It is shown by albumin solution which remained clear after dropped with the test solution. While some test solution containing heavy metal cations show positive denaturation protein. The use of heavy metals in cosmetics is very dangerous because it will denature proteins that exist under the skin of collagen. While the gold in the form of ions or nanogold do not denature protein, its presence in cosmetics is safe and not harmful [10].

2. Method
2.1 Tool and Material Beaker, HAuCl4 1 mM, Erlenmeyer, Sodium Citrate 1%, Hot plate and stirer, Pipette volume of 10 mL and 1 mL, Bottle 10 mL. 2.2 Nanogold Synthesis Procedure Setting the equipment of synthesis: Erlenmeyer flask, magnetic stirrer and hot plate. Took 10 mL of gold solution (HAuCl4) and included in the pumpkin, then the temperature is raised to 80 C and the stirrer is run in at 300 rpm for 13 min. Matrix Mono glyceryl stearate is melted and incorporated in the flask followed by a reducing solution of 1 mL of Sodium Citrate. There are some changes during the synthesis took place and noted the changes that occur during the 7 min of synthesis. 2.3 Preliminary Test Procedure for the Implementation of Nanogold on Cosmetics Preliminary test begins with a dilute 10 mL of egg white with aquades until the volume of 200 mL. This solution was subsequently included in the test tube, each of 20 mL. Preparation of 6 test solutions are a solution containing the tested metal cations such as Pb2+ solution, a solution of Hg2+, Cd2+, Au3+, Na+ and Au solution (nanogold). Each the tube reactin solution contains 20 mL dilute solution of albumin. Drop 0.5 mL of test solution (10 drops) into each reaction tube that already contains a dilute solution of albumin. Observations were done on each test tube, where the observed is whether the albumin in each reaction tube having denaturation. If albumin denatured then test the metal is not safe for cosmetics. This is because the skin contains a protein that is well below the skin layer which is a secretion from skin cells of collagen. When cosmetics contain heavy metals, it is possible to experience skin collagen denaturation and damage to the formation of collagen metabolism. Thus, the skin will experience a disruption of collagen

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Nanogold Synthesis Using Matrix Mono Glyceryl Stearate as Antiaging Compounds in Modern Cosmetics

formation resulting in the appearance of wrinkles or premature aging.

3. Results and Discussion

3.1 Nanogold Synthesis Results Nanogold synthesis results in a matrix glycerin mono stearate were analyzed using SEM-EDX instrument which provides spectra in Figs. 1 and 2. Synthesis nanogold performed using glycerin monostearate matrix because this material is one of the basic constituent cream commonly used in the manufacture of pharmaceutical preparations for cosmetic cream. These materials are also used for mixing with cosmetics that will be made easier and produce a homogeneous pharmaceutical ingredient. Use of the matrix is also intended to be a successful synthesis of nanogold, because the matrix will help prevent the occurrence of precipitation. Basically, synthesis through bottom-up process is a process of reduction of gold cations into gold nanomaterial or nanogold. Gold cations in the form of AuCl4- are reduced by sodium citrate to produce Au atom that would soon join the others in the number oftens, thousands or even millions. These atoms will soon interact with the strong metal bonding. The molecules of the matrix will hold a collection of atoms or clusters to grow steadily or limit the growth of gold clusters to be retained in a certain amount. This control is important. If not controlled, the cluster will grow continuously until a certain size and weight that can no longer be in the form of colloid or solution. Large clusters will fall as sediment and nano-size exceeded. Thus the material obtained in the micro scale even in the size of the meter. Thats why the use of gold as a cosmetic, it is necessary to develop the synthesis of nanogold in a matrix of glycerin monostearate. Nanogold synthesis results give the same form clusters with the standard of nanogold image that has been used in metal plating, but in a different size magnification. Visible matrix that gives glyceryl monostearate layers between the gold clusters are

Fig.

Synthesis result (5.000 x).

Fig.

2 Standard picture of nanogold.

scattered in the folds of the matrix. The matrix is an organic material that can be easily damaged by high energy visible on magnification 20.000 that require high energy matrix is burned and the spectra became dark. Standard picture that does not use matrix in the synthesis was flat and homogenous. The size of nanogold cluster of synthesis is in the range 80-200 nm, where the material that was agreed as nano material has a size of 10-100 nm. Thus, the results of synthesis are partly already in the range of nanoscale materials and some larger than nanoscale materials. For use in cosmetics sizes 80-200 nm are still acceptable, because the pores of the skin has a much larger size of the micro or mesoscale. Particle size for cosmetics is in the range 10-800 nm, so that the result of the synthesis is still in accordance with the particle range of

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cosmetics. Nevertheless have to look for other matrices in the synthesis in order to obtain the results of synthesis in the nano size, so the catalytic effect is given to a maximum. Glyceryl monostearate has a small molecular size and shape of molecules that are less filled the space where only one fatty acid bound in glycerol. The shape and size of the matrix will determine the size of the resulting gold clusters. Similarly, the concentration of the matrix also affects the size of the resulting gold clusters. The greater, the more fill the space and the higher density matrix will leave small spaces that limit the accumulation of gold atoms of the reduction. Thus,

the resulting clusters are small because of spaces remaining too small. The concentration of glyceryl monostearate used in this synthesis is 0.2% which produces gold clusters with sized of 80-200 nm. Matrix concentration can be increased to produce a smaller gold clusters (Fig. 3). The results of SEM-EDX instruments analysis provide information that the synthesis of nanogold in matrix of glyceryl mono stearate contain nanogold 9.48%. However, this percentage is still increasing due to carbon coating in sample preparation led to an increase in carbon content and reduced content of nanogold.

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Nanogold Synthesis Using Matrix Mono Glyceryl Stearate as Antiaging Compounds in Modern Cosmetics

Fig. 3

Positive test of protein denaturation.

3.2 Preliminary Test Results for the Implementation of Nanogold on Cosmetics Metals such as Pb, Hg, and Cd in the form of cations can cause denaturation of proteins. Dilute solution of egg albumin which had denaturation due to metal ions changed from transparent colorless to be like a white mist. For the same concentration, Pb is the most powerful to denaturation of albumin solution followed by Hg and Cd. Thus, it is recommended that the three metals are not safe for cosmetics (Fig. 3). In fact, these dangerous metals are still found in many types and brands of cosmetics, primarily for cosmetic colorant in the form of complex molecules. Pb is a very common cosmetic dye because the complex Pb gives a strong color and not easily fades.

Similarly, the metallic Hg is still widely used in cosmetic whitening groups that provide very fast results. The use of cosmetics containing mercury in less than two week shave produced a very clear change, where the dark skin would be white. Generally, mercury is not safe for skin and body health. These metals can form strong bonds with fat tissue and extremely difficult to remove, so the resulting skin damage is difficult restored. Mercury is also able to penetrate the dermis of the skin tissue and even deeper into the blood circulation. When using these dangerous cosmetics still continues, mercury is also able to penetrate various tissues and can lead to impaired fetal growth and even cause miscarriage. Mercury can damage the developing fetus by performing denaturation of lipoprotein constituent

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organs and tissues of the fetus. Therefore it need to be aware of this dangerous cosmetic circulation in society, especially when there are warnings in the cosmetic use of termination if the user is pregnant. It should be suspected that these cosmetics contain these harmful metals. Cadmium was also found as a dye in cosmetics. The metal which can also cause denaturation of the proteins has also the ability to penetrate skin tissue, although not as strong as mercury. The use of cadmium as lipstick dyes can cause irritation to flake layer of lip skin. Discontinuation will affect the gradual recovery. This is very different from the effects of cosmetics containing mercury, in which the termination will cause damage, respiratory problems, and even death. Cessation of the use of creams containing mercury can cause a sudden appearance of black spots. This is a typical phenomenon that is very easily observed. The observations give the following test results that the solution gives a negative result means a dilute solution of albumin did not experience denaturation with test solution include a solution of Au3+, Na+ solution and a solution of Au (nanogold). Albumin solution that remains transparent do not experience denaturation. This indicates that the presence of metal is safe in cosmetics because it will not harm the skin protein which is collagen (Fig. 4). Some research results related to the use of metallic gold has been patented, such as a dye that is safe for modern cosmetics. Patents related to the utilization of nanogold as dyes of various types of cosmetics that is U.S. patent number U.S. 0022765 in claims by Chung

et al published 22 January 2009. Thus, it is precisely when the gold metal is used as a dye in modern cosmetics [11]. The next patent related to the use of nanogold is U.S. 0022765 which was claimed by Pop issued on May 12, 2011. Gold nanoparticles are designed specially to touch and penetrate the cell, nucleus, or metokondria membrane of target cells by making the nanogold complex with a structure that can resonate and vibrate with specific frequencies to carry and release glutathione into the target cell. Thus, the gold metal in the form of nanoparticles are safely into the human body so it is safe for cosmetics [12]. It is time the modern cosmetic use of safe materials and provides great benefits to the compounds of the essential results of research development. Development of synthesis of nanogold becomes very important to be immediately applied in cosmetic products as an anti-aging material. Besides safe for health, nanogold also has activity as a cofactor of enzymes that help the formation of skin collagen and collagen in other tissues. Regeneration of collagen is an important process for maintaining youthful skin. Damage to collagen that occurs naturally, can be inhibited by the continuous regeneration of collagen. This is the basic use of nanogold as an important material in modern anti-aging cosmetics. Nanoscale forms also provide a catalytic effect that increased 20-200 times compared to the size of the micro-meter. Therefore, the development of the synthesis of nanoscale materials in the form of nanogold is becoming very important [13].

Fig. 4 Negative test of protein denaturation.

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Nanogold Synthesis Using Matrix Mono Glyceryl Stearate as Antiaging Compounds in Modern Cosmetics [4] [5] [6] [7] G.C. Bond, D. Thompson, Catalysis by gold, Catal. Rev. Sci. Eng. 41 (1999) 319. A.S.K. Hashimi, Homogeneous catalysis by gold, Gold Bull. 37 (2004) 51. A. Hoffmann-Rider, N. Krause, The golden gate to catalysis, Org. Biomol. Chem. 3 (2005) 387. A.S.K. Hashimi, R. Salath, T.M. Frost, L. Schwarz, J.H. Choi, Homogeneous catalysis by gold: the current status of C,H activation, Appl. Catal. A: General 291 (2005) 238. A.S.K. Hashimi, L. Schwarz, J.H. Choi, T.M. Frost, A new gold-catalyzed C-C bond formation, Angew. Chem. 39 (2000) 2285. Y. Fuchita, Y. Utsunomiya, M. Yasutake, Synthesis and reactivity of arylgold(III) complexes from aromatic hydrocarbons via C-H bond activation, J. Chem. Soc., Dalton Trans. (2001) 2330. M.T. Reetz, K. Sommer, Gold-catalyzed hydroarylation of alkynes, Eur. J. Org. Chem. (2003) 3485. B.H. Chung, Cosmetic pigment composition containing gold or silver nano particles, United States Patent Application Publication, Pub. No: US 2009/0022765 A1, Pub Date: Jan. 22, 2009. C.V. Pop, Transport and delivery of glutathione into human cells using gold nanoparticles, United States Patent Application, Pub No: US 2011/0111022 A1, Pub. Date: May 12. 2011. Wolf et al, SP1 polypeptides, modified SP1 polypeptides and uses thereof, United States Patent Application, Pub No: US 2009/0062197 A1, Pub. Date: Mar. 5, 2009.

4. Conclusions
The results showed that the nanogold can be safely used in cosmetics because it does not destruct proteins as heavy metals Pb, Hg and Cd, so the use of nanogold in cosmetics, especially for antiaging is strongly recommended. Nanogold synthesis results in a matrix of glyceryl monostearate has succeeded where the synthesis has a morphology similar to the previous synthesis results without using a matrix, which has been used as a coating of metal nano-materials. Matrix was evident in the SEM-EDX spectra of the folds between nanogold clusters formed while in the standard picture is not visible. The content of nanogold in the matrix glyceryl mono stearate is 9.48% shown by SEM-EDX spectra.

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